CN1172934C - Process for preparation of 2-amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine - Google Patents
Process for preparation of 2-amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine Download PDFInfo
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- CN1172934C CN1172934C CNB018111696A CN01811169A CN1172934C CN 1172934 C CN1172934 C CN 1172934C CN B018111696 A CNB018111696 A CN B018111696A CN 01811169 A CN01811169 A CN 01811169A CN 1172934 C CN1172934 C CN 1172934C
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- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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Abstract
2-Amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]-pyrimidine is prepared from a 5-chloro or 5-methoxy substituted 3-amino-8-methoxy[1,2,4]triazolo[4,3-c]-pyrimidine by reaction with methoxide in an alcohol solvent. Both rearrangement and, when the 5-substituent is chloro, methoxy substitution can be accomplished directly.
Description
The present invention relates to prepare 2-amino-5, the method for 8-dimethoxy [1,2,4] triazole [1,5-c] pyrimidine.
United States Patent (USP) 5,858,924 describe some substituted benzene sulfonic acid amide compound and they as herbicide applications.2-amino-5,8-dimethoxy [1,2,4] triazole [1,5-c] pyrimidine are the useful intermediates of these weedicides of preparation.
United States Patent (USP) 5,858,924 by handling with ethyl acrylate and the sodium methylate in methyl alcohol, prepares 2-amino-5 from 3-amino-8-methoxyl group-5-methylthio group [1,2,4] triazole [4,3-c] pyrimidine, 8-dimethoxy [1,2,4] triazole [1,5-c] pyrimidine.Use 5-methoxyl group-4-chloro-2-methylthio group-pyrimidine and hydrazine reaction successively, prepare 3-amino-8-methoxyl group-5-methylthio group [1,2,4] triazole [4,3-c] pyrimidine with the cyanogen bromide cyclisation then.Prepare 2-amino-5 with more effective, the higher production of productive rate, 8-dimethoxy [1,2,4] triazole [1,5-c] pyrimidine is favourable.And have and avoid using the first sulphur compound that contains intermediate, avoid resetting the advantage that forms use ethyl propenoate in [1,2,4] triazole [1,5-c] pyrimidine at [1,2,4] triazole [4,3-c] pyrimidine.
The present invention relates to prepare 2-amino-5,8-dimethoxy [1,2,4] triazole [1,5-c] pyrimidine from 3-amino-8-methoxyl group [1,2,4] triazole [4,3-c] pyrimidine of 5-chlorine or the replacement of 5-methoxyl group.More particularly, the present invention relates to prepare structural formula as
The method of compound, it comprise with structural formula as
Wherein Z represents Cl or OCH
33-amino-8-methoxyl group-[1,2,4] triazole [4,3-c] pyrimidine and the reaction of the sodium methylate in the alcoholic solvent or potassium methylate.
The present invention relates to preparation on the other hand
Method, this method comprises following a few step:
A) with structural formula as
Wherein Z represents Cl or OCH
35-methoxyl group-4-chloropyrimide and hydrazine and a kind of alkali reaction, the preparation structural formula as
5-methoxyl group as defined above-4-pyrimidine hydrazine of Z wherein.
B) make 5-methoxyl group-4-pyrimidine hydrazine and mauguinite or cyanogen bromide reaction prepare structural formula as
3-amino-8-methoxyl group [1,2,4] triazole [4,3-c] pyrimidine as defined above of Z wherein.
C) with sodium methylate in 3-amino-8-methoxyl group [1,2,4] triazole [4,3-c] pyrimidine and the alcoholic solvent or potassium methylate reaction.
By with alcoholic solvent in sodium methylate or potassium methylate reaction, structural formula as
Wherein Z represents Cl or OCH
33-amino-8-methoxyl group [1,2,4] triazole [4,3-c] pyrimidine be rearranged into 2-amino-5,8-methoxyl group [1,2,4] triazole [1,5-c] pyrimidine.
Z is represented OCH
3, the methylate of a kind of effective catalytic amount of needs, for example, [1,2,4] triazole [4,3-c] pyrimidine of every mole need from 0.01 to 0.5 normal methylate., this ratio depends on the concentration of methylate, generally preferably uses 0.1 to 0.5 normal methylate.
Concerning Z represents Cl, need an extra normal methylate to follow and transform chlorine substituent to a methylate substituting group.Like this, in this case, from 1.1 to 1.5 normal methylates preferably.
Reset and generally carry out as solvent with methyl alcohol.Also can use other primary alconol and secondary alcohol, still, depend on reaction conditions, the alkoxide exchange of a significant quantity can occur in the 5-position of triazolo pyrimidine.Sterically hindered alcohol, for example the tertiary alcohol resembles the trimethyl carbinol and tert-pentyl alcohol, can be used as solvent, and the result causes a spot of or does not have the alkoxide exchange.Yet methyl alcohol generally is preferred solvent.If thinner is a unreactiveness not with desired reacting phase mutual interference and to reactant, especially methyl alcohol is saline and alkaline, also might reset under the condition that extra thinner exists.A kind of special suitable extra thinner is an acetonitrile, and it is through being commonly used for the solvent of preparation [1,2,4] triazole [4,3-c] pyrimidine.
The temperature that rearrangement is carried out is the reflux temperature from 0 ℃ to alcoholic solvent.General preferred temperature is from 10 ℃ to 35 ℃.
Product uses conventional technology as separating by sedimentary or crystalline filtration of material.
In a typical reaction, 3-amino-8-methoxyl group [1,2,4] triazole [4,3-c] pyrimidine that 5-chlorine or 5-methoxyl group replace is dissolved in or is suspended in the alcohol and handles with the sodium methylate that is dissolved in methyl alcohol of appropriate amount at ambient temperature.After reaction was finished, reaction mixture dilute with water and precipitated product were collected and drying with filtering.Optionally, before filtration, can remove some or most of alcohol and improve crystalline and filter or reduce the solubility of product in solvent, increase the rate of recovery thus by distillation.
3-amino-8-methoxyl group [1,2,4] triazole [4 that 5-chlorine and 5-methoxyl group replace, 3-c] pyrimidine can be easily from corresponding 2,4-two chloro-5-methoxy pyrimidine (Chesterfield, J., Mcomie, J.F.W., Sayer, E.R., " pyrimidine .Part VIII. halo-and hydrazine-pyrimidine " J.Chem.Soc.1955,3478-3481) and 2,5-dimethoxy-4 '-chloro-pyrimidine respectively by a) with hydrazine and alkali reaction b then) with mauguinite or cyanogen bromide reaction preparation.
In the process of step a) and hydrazine reaction, need in the alkali and the HCl that produces.This alkali can be the hydrazine of extra equivalent itself.But, often preferably use a kind of auxiliary alkali such as yellow soda ash or salt of wormwood, sodium hydroxide or potassium hydroxide or trialkylamine.Yellow soda ash is preferred auxiliary alkali.
With the cyclization step b) of halogen cyan in, produce hydrogen halide.Extra methylate by using q.s is as the hydrogen halide that alkali neutralizes and discharges, and might finish that methoxyl group replaces and/or as the rearrangement of the actuating section of cyclization.The change of this process has the advantage of avoiding separating [1,2,4] triazole [4,3-c] pyrimidine.
Following listed examples is used to explain the present invention.
Embodiment
1. prepare 2,5-dimethoxy-4 '-pyrimidine hydrazine
4-chloro-2 in methyl alcohol (15 milliliters), the slurries of 5-dimethoxypyridin (3.0 gram, 17.2 mmoles) are handled with the hydrazine water solubles (3.9 grams, 35 weight percents, 42.5 mmoles) and are caused slowly heat release to 29 ℃ of part.Reaction is heated to 50 ℃ then, and remains on this temperature following 2 hours, and this moment, the reaction of gas-chromatography (GC) analysis revealed was carried out fully.Clear soln is cooled to envrionment temperature, and its stirring is spent the night.The decorating film CH of viscosity removed and obtains by solvent with vacuum
3CN (50 milliliters) grinds.The mixture that obtains filters by unmodified packed column (6 centimetres of 6 cm x).Unmodified packed column CH
3CN (550 milliliters) flushing.Filtrate is mixed and solvent is removed with vacuum, obtains the title solid chemical compound (2.6 grams, 89%) of white: fusing point 115-117 ℃;
1H NMR (300 MHz, DMSO-d
6) 3.73 (s, 3H), 3.76 (s, 3H), 4.29 (bs, 2H), 7.51 (s, 1H), 8.23 (bs, 1H); MS (GC, 70eV), 170 (M+, 100%), 155 (55%), 151 (40%).
2. prepare 2-chloro-4-hydrazine-5-methoxyl group-pyrimidine
Anhydrous sodium carbonate (5.83 gram, 0.055 mole), the methyl alcohol (60 milliliters) and 35% the hydrazine water solubles (11.0 grams, 0.120 mole) join 500 milliliters thermometer are installed, and magnetic stirring apparatus is in the there-necked flask of condenser and extra funnel.Dropwise adding is dissolved in 2 of toluene (30 milliliters), and the solution/part slurries of 4-two chloro-5-methoxyl group-pyrimidines (17.91 grams, 0.100 mole) were above 39 minutes.In the process that adds, temperature of reaction rises to 39 ℃ and a kind of clarifying flaxen solution of solid dissolving formation from 15 ℃.Reaction mixture is heated to 42 ℃ and kept 4.1 hours, then removes thermal source.Dropwise add entry (180 milliliters) lentamente, product is crystallized out from solution.The slurries that obtain at room temperature stirred 2 hours, and product uses a B and aspirator vacuum to reclaim by Whatman #1 filter paper filtering then.After washing filter cake with water, product spends the night 40 ℃ of vacuum-dryings, obtains the 2-chloro-4-hydrazine-5-Sulfamonomethoxine (purity 96.2%, productive rate=82.8%) of 15.02 gram whites:
1H NMR (300MHz, DMSO-d
6) 3.33 (s, 3H), 3.78 (s, 3H), 4.39 (brs, 2H), 7.59 (s, 1H), 8.73 (br s, 1H).
3. prepare 2-chloro-4-hydrazine-5-methoxyl group-pyrimidine
Anhydrous sodium carbonate (29.15 grams, 0.275 mole), methyl alcohol (300 milliliters), with 35% the hydrazine water solubles (54.9 grams, 0.60 mole) join 1 liter heat connection thermometer probe is installed, the upper end stirrer of glassed agitator is in the glass jacket reactor of a condenser and a programme controlled circulator bath.2,4-two chloro-5-methoxy pyrimidines (89.50 grams, 0.50 mole) surpass 70 minutes with the increment adding in a small amount of solid mode, and in the adition process, reactor jacket remains on 20 ℃, and temperature of reaction rises to 28 ℃ from 21 ℃.After the adding reaction was finished, reaction mixture was heated to 43 ℃, surpassed 60 minutes, kept 43 ℃ to 4.5 hours then.Add entry (300 milliliters), still head is received on the reactor.Use vacuum to reduce pressure, and remove methyl alcohol with distillation to 140mmHg.Distillation continues 1.5 hours, and at this moment, distillation rate slows down very soon.Pressure further is reduced to 85mmHg and begins distillation up to water, removes vacuum with nitrogen gas stream then.Reaction mixture is cooled to 25 ℃ above 60 minutes from 43 ℃.The slurries that obtain stir down at 25 ℃ and spend the night.Product uses a B and aspirator vacuum to reclaim by Whatman #52 filter paper filtering then.Behind water (221 gram) washing leaching cake, product spends the night 42 ℃ of vacuum-dryings, obtains the 2-chloro-4-hydrazine-5-Sulfamonomethoxine (purity 96.8%, productive rate=92.7%) of 83.5 gram whites.
4. prepare 3-amino-5-chloro-8-methoxyl group [1,2,4] triazole [4,3-c] pyrimidine
One is equipped with thermowell and a condenser/N2 outlet is housed, 5 liters of 3-mouth round-bottomed flasks of a mechanical stirrer and an addition funnel, 2-chloro-4-hydrazine-5-methoxy pyrimidine (136 grams, 70.7% weight percent, 96 grams are active, 0.55 mole) and Virahol (IPA wherein are housed; 1100 milliliters).(34.6% weight percent of 185 grams is at CH to add cyanogen bromide fast
3CN, 64 grams are active, 0.6 mole) cause slow heat absorption, make from 22 to 15 ℃ of temperature, a very slow heat release makes temperature reach 27 ℃ then.In exothermic phase, mixture continues several minutes through heavy-gravity stage very.Slurries are heated to 42 ℃, kept 3.5 hours, during carry out high pressure liquid chromatography (HPLC) and analyze, show to react completely.The slurries cool to room temperature is with Na
2CO
3Solution reaction (Na
2CO
364 grams, 0.6 mole, 1100 milliliters in water) 30 minutes, make temperature exotherm to 4 ℃.Mixture stirred 2 hours at ambient temperature, then solid collected by filtration.Filter cake water (400 milliliters) washing press dry under swabbing pressure then as much as possible.The brown solid of the title compound that obtains (the wet cake of 190.1 grams records 51 weight % by HPLC, and 97 grams are active, 88%).Sample drying obtains following data: MS (GC, 70eV) 201 (15%), 200 (30%), 199 (70%), 198 (100%) to constant weight;
1HNMR (300MHz, DMSO-d
6), 3.92 (s, 3H), 6.51 (br s, 2H), 7.11 (s, 1H).
5. the preparation of 3-amino-5-chloro-8-methoxyl group [1,2,4]-triazole [4,3-c] pyrimidine
2-chloro-4-hydrazine-5-methoxy pyrimidine (10.75 grams, 0.062 mole) is packed into condenser is housed, in the there-necked flask of thermometer and overhead stirrer.Add IPA (125 milliliters), use ice bath that mixture is cooled to 13 ℃.By sleeve pipe mauguinite is added as condensing agent.Reaction mixture is heated to 41 ℃, continues 3.5 hours, then cool to room temperature.Add aqueous sodium carbonate (yellow soda ash 7.18 grams, 125 milliliters in water), mixture stirring at room 2 hours to remove remaining mauguinite, neutralized salt hydrochlorate.Use B and vacuum aspirator, by Whatman#54 filter paper, the filtered and recycled product washes with water, and the vacuum drier inner drying spends the night, and obtains 9.65 gram title compounds (productive rate=78.5%).
6. prepare 3-amino-5,8-dimethoxy [1,2,4]-triazole [4,3-c] pyrimidine
4-hydrazine-2,5-dimethoxypyridin (8.522 grams, 0.050 mole) is packed into 500 milliliters overhead stirrer is housed, in the there-necked flask of condenser and electric thermo-couple temperature detector.Add IPA (100 milliliters), mixture stirs into slurries.Add cyanogen bromide (0.081 mole of 8.546 gram are dissolved in 15 milliliters of acetonitriles), make and absorb heat, then heat release to 6 ℃ to 3 ℃.Mixture heating up to 42 ℃ continues 3.5 hours, then cool to room temperature.Add sodium carbonate solution (5.92 grams, 100 milliliters in water), the mixture that obtains stirred 3.3 hours.Product precipitates from solution, uses B and vacuum aspirator, by Whatman#54 filter paper, and the filtered and recycled product.Solid room temperature vacuum drier inner drying spends the night, and obtains 3-amino-5,8-dimethoxy [1,2,4]-triazole [4,3-c] pyrimidine (productive rate=87.1%): mp=232-235 ℃.
1H?NMR(300MHz，DMSO-d
6)3.83(s，H)，3.97(s，3H)，6.45(br?s，2H)，6.84(s，1H)；
13CNMR(75.47MHz，DMSO-d
6)，55.4，56.4，115.5，139.7，142.0，142.5，148.3。
7. 2-amino-5, the preparation of 8-dimethoxy [1,2,4]-triazole [1,5-c] pyrimidine
3-amino-5,8-dimethoxy [1,2,4]-triazole [4,3-c] pyrimidine (9.762 grams, 0.050 mole) is packed into 500 milliliters overhead stirrer is housed, and condenser is in the there-necked flask of addition funnel and electric thermo-couple temperature detector.Add methyl alcohol (70 milliliters), mixture stirs into slurries.Sodium methylate (16.716 grams form content and be 25% methanol solvate) dropwise added in 28 minutes, and mixture was stirring at room 3 hours then.Reaction mixture water (135 milliliters) dilution, restir 1.5 hours.Solid phase prod uses B and vacuum aspirator, by Whatman#54 filter paper, filtered and recycled.After washing with water, solid room temperature vacuum drier inner drying spends the night, and obtains 2-amino-5,8-dimethoxy [1,2,4]-triazole [1,5-c] pyrimidine (productive rate=92.8%):
1H NMR (300Hz, DMSO-d
6) 3.88 (s, 3H), 4.04 (s, 3H), 6.38 (brs, 2H), 7.48 (s, 1H); MS (GC, 70eV) 195 (M+, 85%), 194 (100%).
8. 2-amino-5, the preparation of 8-dimethoxy [1,2,4]-triazole [1,5-c] pyrimidine
2-chloro-4-hydrazine-5-methoxy pyrimidine (the pure chlorination hydrazine methoxy pyrimidine of the 15.62 grams 83.8%=actual chlorination hydrazine methoxyl group-pyrimidine of 13.09 grams, 0.075 mole) pack into 500 milliliters magnetic stirring apparatus be housed, condenser is in the there-necked flask of thermometer and addition funnel.Add the trimethyl carbinol (150 milliliters), mixture stirs and obtains white slurries.In surpassing 13 minutes, dropwise add cyanogen bromide solution (8.78 grams, are dissolved in 20 milliliters of acetonitriles by 0.083 mole).Mixture temperature drops to 22 ℃ from 23 ℃.Reaction mixture is heated to 43 ℃ then, continues 5.2 hours.Reaction mixture (faint yellow slurries) is careful passes through teflon
TM(Teflon
TM) sleeve pipe pass to second be equipped with 25% sodium methylate (be dissolved in methyl alcohol, 41.5 the gram, 0.188 mole) there-necked flask in.Transmission was carried out 52 minutes, made temperature of reaction bring up to maximum 42 ℃ from 21 ℃.The reaction mixture that obtains is the pausiaceous slurries of deceiving.After addition is finished 2 minutes, sample thief was with HPLC analysis revealed intermediate product 3-amino-5-chloro-8-methoxyl group [1,2,4]-triazole [4,3-c] pyrimidine 99% finishes the final product 2-amino-5 that is converted into expection, 8-dimethoxy [1,2,4]-triazole [1,5-c] pyrimidine.After 30 minutes, reaction mixture water (300 milliliters) washing 12 minutes.The slurries that obtain stirred 1 hour, used B and vacuum aspirator then, by Whatman#54 filter paper, and the filtered and recycled solid.Solid washes with water, and 48 ℃ of vacuum drier inner dryings spend the night, and obtains grey Bi Lanse solid (11.99 restrain 91.3% pure 2-amino-5,8-dimethoxy [1,2,4]-triazole [1,5-c] pyrimidine, productive rate 74.7%).
9. 2-amino-5, the preparation of 8-dimethoxy [1,2,4]-triazole [1,5-c] pyrimidine
2-chloro-4-hydrazine-5-methoxy pyrimidine water wets, and (83.2 grams, 84.0% chlorination hydrazine methoxy pyrimidine=69.84 restrain actual chlorination hydrazine methoxy pyrimidine to cake, 0.4 mole) pack into 1 liter the electric thermo-couple temperature detector be housed, the overhead stirrer that has the glass vibrator, condenser, the jacketed reactor of addition funnel and water-bath capable of circulation.Add the trimethyl carbinol (700 milliliters) and methyl alcohol (100 milliliters), mixture stirs, and obtains white slurries.In 20 minutes, dropwise add cyanogen bromide solution (47.19 grams, are dissolved in 105 milliliters of acetonitriles by 0.445 mole).The reaction mixture slurry retrogradation, mixture temperature is brought up to 29 ℃ from 23 ℃.Reactor jacket was heated to 41 ℃ from 22 ℃ in 55 minutes, kept 6.2 hours at 41 ℃ then.During this period, monitoring reaction, slurries were thinning when reaction was carried out.When intermediate triazole [4,3-c] when pyrimidine is completed into, use peristaltic pump, by the PTFE suction pipe reaction mixture (faint yellow slurries) is transferred in 2 liters the there-necked flask that 30% sodium methylate (being dissolved in methyl alcohol, 181.0 grams, 1.00 moles) be housed.2 liters flask cools off with ice bath.Transfer was carried out 52 minutes, caused temperature of reaction to bring up to maximum 28 ℃ from 21 ℃.Transmit fully, the extra methyl alcohol of rinsing transfer pipeline (120 milliliters) enters in the reactor.The reaction mixture that obtains is the pausiaceous slurries of deceiving.After stirring 1 hour at ambient temperature, hydrochloric acid soln (15.1 grams spissated hydrochloric acid be diluted in the 300 ml waters) cancellation of reaction mixture by dropwise adding extra dilution.Use the hydrochloric acid (6.3 gram) of 6N that the pH value of the slurries that obtain is transferred to 8.50.Put still head, under reduced pressure (110mmHg), the distillation of the volatile matter in the reaction mixture is removed.When distillment is removed, add extra water, so that solution is become water from alcohol.Remove 1029 gram distillments altogether, during distilling, add extra 500 ml waters.Mixture slowly cools off, and stirring is spent the night.Use Bu Shi (Buchner) funnel and vacuum aspirator, by Whatman#54 filter paper, the filtered and recycled solid.Solid water (211 gram) washing, 83 ℃ of vacuum drier inner dryings spend the night, brown ceramic powder solid product in obtaining (the pure 2-amino-5 of 66.3 grams 95.7%, 8-dimethoxy [1,2,4]-triazole [1,5-c] pyrimidine, productive rate 82.4%).
Claims (4)
- A structural formula asThe preparation method of compound, this method comprise with structural formula asWherein Z represents Cl or OCH 33-amino-8-methoxyl group-[1,2,4] triazole [4,3-c] pyrimidine and the sodium methylate in the alcoholic solvent or potassium methylate react for the methyl alcohol from 0 ℃ to reflux temperature in temperature.
- 2. the method for claim 1, wherein said alcoholic solvent is a methyl alcohol, perhaps uses separately, perhaps mixes use with the tertiary butyl or tert-pentyl alcohol.
- 3. method as claimed in claim 1 or 2, wherein said structural formula asWherein Z represents Cl or OCH 33-amino-8-methoxyl group-[1,2,4] triazole [4,3-c] pyrimidine prepare by following steps:A) with structural formula as
Wherein the 5-methoxyl group-4-chloropyrimide as defined above of Z and hydrazine and be selected from the alkali reaction of yellow soda ash or potassium, sodium hydroxide or potassium or trialkylamine, the preparation structural formula as5-methoxyl group as defined above-4-hydrazine pyrimidine of Z wherein; AndB) make 5-methoxyl group-4-hydrazine pyrimidine and mauguinite or cyanogen bromide reaction. - 4. method as claimed in claim 3, the wherein said 3-amino-8-methoxyl group-[1 that makes 5-methoxyl group-4-hydrazine pyrimidine and mauguinite or cyanogen bromide reaction preparation, 2,4]-triazole [4,3-c] pyrimidine directly with alcoholic solvent in sodium methylate or potassium methylate be to react the methyl alcohol from 0 ℃ to reflux temperature in temperature, need not to separate, the preparation structural formula asCompound.
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| DE10019291C2 (en) * | 2000-04-19 | 2002-04-04 | Sueddeutsche Kalkstickstoff | 2-alkoxy-5-methoxypyrimidines or their tautomeric forms and processes for their preparation |
| US8038779B2 (en) * | 2006-09-07 | 2011-10-18 | General Electric Company | Methods and apparatus for reducing emissions in an integrated gasification combined cycle |
| CN101486684B (en) * | 2009-02-20 | 2010-11-10 | 常熟华益化工有限公司 | Preparation of 2,4-dichloro-5-methoxy pyrimidine |
| PL2851367T3 (en) * | 2010-05-25 | 2017-05-31 | Dow Agrosciences, Llc | Process for the preparation of a 2-amino-5,8-alkoxy[1,2,4]triazolo[1,5-c]pyrimidine by reaction of a 5-halo-8-alkoxy[1,2,4]triazolo[1,5-c]pyrimidin-2-amine with an alkali metal alkoxide in an alcoholic solvent |
| WO2014043087A1 (en) * | 2012-09-14 | 2014-03-20 | Dow Agrosciences Llc | Process for the preparation of 2-amino-5,8-dimethoxy[1,2,4]triazolo[1,5-c]pyrimidine from 4-chloro-2,5-dimethoxypyrimidine |
| CN103232453A (en) * | 2013-04-18 | 2013-08-07 | 黑龙江大学 | Synthesizing method of 2-amino-5,8-dimethoxy[1,2,4]-triazolo[1,5-c]-pyrimidine |
| CN103880846B (en) * | 2014-03-12 | 2016-09-14 | 泸州东方农化有限公司 | A kind of preparation method of triazolo pyrimidine mercapto radical-type compound |
| CN104961662B (en) * | 2015-06-11 | 2017-05-03 | 湖南化工研究院有限公司 | Preparation method of 2-fluoro-6-trifluoromethyl benzenesulfonyl chloride |
| CN109400538A (en) * | 2018-12-19 | 2019-03-01 | 江苏中谱检测有限公司 | The preparation method of penoxsuam raw medicine related impurities bis-CHYMP |
| CN111848625B (en) * | 2019-04-24 | 2022-07-26 | 江苏恒瑞医药股份有限公司 | Preparation method and intermediate of heteroaryl [4,3-c ] pyrimidine-5-amine compound |
| CN112730689B (en) * | 2020-12-29 | 2023-04-07 | 营口昌成新材料科技有限公司 | Liquid chromatography analysis method of 2-amino-5, 8-dimethoxy [1,2,4] triazolo [1,5-c ] pyrimidine |
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| US4591588A (en) * | 1984-02-24 | 1986-05-27 | Riker Laboratories, Inc. | Triazolo[1,5-c]pyrimidines and bronchodilation use thereof |
| US5667744A (en) * | 1992-12-22 | 1997-09-16 | Focal Point Products, Inc. | Method for fabricating columns |
| US5480991A (en) * | 1993-11-05 | 1996-01-02 | Dowelanco | 2-Alkoxy-4-hydroazinopyrimidine compounds and their use in the preparation of 5-alkoxy-1,2,4-triazolo[4,3-c]pyrimidine-3(2H)-thione compounds |
| DE122009000052I2 (en) | 1996-09-24 | 2009-12-31 | Dow Agrosciences Llc | N - ((1,2,4) TRIAZOLOAZINYL) BENZOLSULFONAMIDE AND PYRIDINSULFONAMIDE COMPOUNDS AND THEIR USE AS HERBICIDES |
-
2001
- 2001-06-15 HU HU0301399A patent/HU228907B1/en not_active IP Right Cessation
- 2001-06-15 AU AU6849701A patent/AU6849701A/en active Pending
- 2001-06-15 AT AT01946446T patent/ATE261971T1/en active
- 2001-06-15 CN CNB018111696A patent/CN1172934C/en not_active Expired - Lifetime
- 2001-06-15 JP JP2002504261A patent/JP4223280B2/en not_active Expired - Fee Related
- 2001-06-15 WO PCT/US2001/019348 patent/WO2001098305A1/en active IP Right Grant
- 2001-06-15 AU AU2001268497A patent/AU2001268497B2/en not_active Ceased
- 2001-06-15 DE DE60102375T patent/DE60102375T2/en not_active Expired - Lifetime
- 2001-06-15 EP EP01946446A patent/EP1289994B1/en not_active Expired - Lifetime
- 2001-06-15 KR KR1020027017066A patent/KR100800982B1/en not_active IP Right Cessation
- 2001-06-15 IL IL15344801A patent/IL153448A0/en active IP Right Grant
- 2001-06-15 DK DK01946446T patent/DK1289994T3/en active
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- 2001-06-15 TW TW090114602A patent/TWI271405B/en not_active IP Right Cessation
- 2001-06-15 BR BR0111993-1A patent/BR0111993A/en not_active Application Discontinuation
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|---|---|
| KR20030010715A (en) | 2003-02-05 |
| IL153448A0 (en) | 2003-07-06 |
| DE60102375T2 (en) | 2004-07-29 |
| EP1289994B1 (en) | 2004-03-17 |
| IL153448A (en) | 2006-10-31 |
| AU2001268497B2 (en) | 2005-08-11 |
| ZA200210035B (en) | 2003-12-11 |
| DK1289994T3 (en) | 2004-06-21 |
| CN1436190A (en) | 2003-08-13 |
| BR0111993A (en) | 2003-04-01 |
| KR100800982B1 (en) | 2008-02-05 |
| HU228907B1 (en) | 2013-06-28 |
| US6362335B2 (en) | 2002-03-26 |
| HUP0301399A2 (en) | 2003-08-28 |
| EP1289994A1 (en) | 2003-03-12 |
| JP2004501156A (en) | 2004-01-15 |
| DE60102375D1 (en) | 2004-04-22 |
| US20020013230A1 (en) | 2002-01-31 |
| TWI271405B (en) | 2007-01-21 |
| AU6849701A (en) | 2002-01-02 |
| HUP0301399A3 (en) | 2009-01-28 |
| WO2001098305A1 (en) | 2001-12-27 |
| JP4223280B2 (en) | 2009-02-12 |
| ATE261971T1 (en) | 2004-04-15 |
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